KR101876155B1 - Vibration-damping urethane resin composition, vibration-damping molded urethane resin object, and method for forming said molded object - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a damping urethane resin composition, a vibration damping urethane resin molding, and a method of forming the damping urethane resin composition. The damping urethane resin composition comprises a castor oil polyol (A), an isocyanate (B) And contains particles (C).

Description

[0001] The present invention relates to a vibration-damping urethane resin composition, a vibration-damping urethane resin molding, and a vibration-damping urethane resin composition,

The present invention relates to a vibration damping urethane resin composition, a vibration damping urethane resin molding, and a method for forming the damping resin.

A filler having excellent resistance to load and heat resistance has been used in the lower part of a ship engine for accurate and simple installation of equipment. However, since this filler has no vibration damping property, there has been a fear of engine component damage due to vibration of the engine. Therefore, the application of vibration damping material to the lower part of the ship engine is being investigated so that the vibration of the engine is not transmitted to the engine parts.

On the other hand, rubber-based flexible materials and vibration damping urethane resin compositions are generally used as vibration damping materials.

As such a damping material, for example, Patent Document 1 discloses a material containing an acrylic urethane resin.

Patent Document 2 discloses a resin composition containing particles and a binder resin capable of absorbing, reducing and suppressing vibration energy, and discloses a core-shell particle having a shell made of a crosslinked resin as the particle.

Japanese Patent Application Laid-Open No. 2005-289043 Japanese Patent Application Laid-Open No. 2006-335279

The conventional vibration damping material is poor in resistance to mechanical stress such as abrasion and impact and plastic deformation due to heat in addition to load resistance, heat resistance, hydrolysis resistance and acid resistance, so that a large load is applied They were not suitable for the portions used in a high temperature atmosphere.

Further, since the molded article obtained from the vibration damping resin composition comprising the microcapsule having the outer shell formed of the organic resin or the porous article formed of the organic resin has a very strong outer shell structure, it is difficult to be deformed, and the vibration energy is converted into thermal energy There was a problem that it was difficult.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a resin composition which is excellent in creep resistance and can easily form a molded article having a large loss coefficient.

As a result of intensive studies for solving the above problems, the present inventors have found that the above object can be achieved by a resin composition containing a castor oil-based polyol, isocyanate and specific inorganic particles, and completed the present invention.

Examples of the construction of the present invention are the following [1] to [16].

[1] A damping urethane resin composition comprising a castor oil-based polyol (A), an isocyanate (B) and an inorganic particle (C) containing a phase-change material.

[2] The damping urethane resin composition according to [1], wherein the hydroxyl value of the castor oil-based polyol (A) is 300 mgKOH / g or more and the number of functional groups is 3 or more.

[3] The vibration damping urethane resin composition according to [1] or [2], wherein the viscosity of the castor oil-based polyol (A) at 25 ° C is 8,000 mPa · s or less.

[4] The vibration damping urethane resin composition according to any one of [1] to [3], which contains 1 to 25 mass% of the inorganic particles (C).

[5] The damping urethane resin composition according to any one of [1] to [4], wherein the phase-change material is at least one selected from paraffin, wax, fatty acid and polyalkylene glycol.

[6] The vibration damping urethane resin composition according to any one of [1] to [5], wherein the phase-change material has a melting point of -30 to 200 ° C.

[7] The damping urethane resin composition according to any one of [1] to [6], wherein the isocyanate (B) is at least one selected from carbodiimide-modified diphenylmethane diisocyanate and tolylene diisocyanate.

[8] The vibration damping urethane resin composition according to any one of [1] to [7], further containing an inorganic pigment (D).

[9] The vibration damping urethane resin composition according to any one of [1] to [8], further containing a flame retardant (E).

[10] The vibration damping urethane resin composition according to any one of [1] to [9], further containing an additive (F).

[11] The vibration damping urethane resin composition according to any one of [1] to [10], which is a two-pack type.

[12] A vibration damping urethane resin molded article formed from the vibration damping urethane resin composition according to any one of [1] to [11].

[13] A vibration damping urethane resin molded article satisfying the following requirements (1) and (2).

(1) The loss factor (tan?) At 80 DEG C and 1 Hz is 0.4 or more

(2) a creep change rate of 25% or less when a load of 4.5 MPa is applied at 70 DEG C for one week

[14] The damping urethane resin molded article according to [13], which further satisfies the following requirement (3).

(3) The flammability meets the HB standard of UL94 standard.

[15] The vibration damping urethane resin molded article according to any one of [12] to [14], which is used under the engine of a ship.

[16] A method for forming a vibration damping urethane resin molded article, which comprises a step of pouring the vibration damping urethane resin composition according to any one of [1] to [11] into a construction site to form a molded article.

According to the present invention, it is possible to obtain a vibration damping urethane resin composition which is excellent in creep resistance and can easily form a molded article having a large loss coefficient. Since the molded article formed from such a resin composition has high vibration damping effect, excellent resistance to compression load and impact resistance, and less plastic deformation due to heat, it is suitable even under extremely severe conditions such as high load such as under the engine, Can be used.

Further, according to the present invention, since a vibration-proof urethane resin composition exhibiting high fluidity can be obtained even in a solventless system, a molded article can be formed by pouring or the like. Therefore, by using the vibration damping urethane resin composition of the present invention, a molded article having the above effect can be formed at a desired place (even with a slight gap for fixation of equipment, etc.), and a molded article The load on the environment can be reduced.

Since the composition of the present invention has the above effect, it is necessary to fix the device under high load and high temperature atmosphere in order to fix the device and the like. Further, it is required to have vibration damping property, For example, it can be suitably used as a composition for forming a molded body for fixing the bottom of a marine engine.

Further, according to the composition of the present invention including the flame retardant, a molded article having excellent creep resistance and a large loss factor as well as excellent flame retardancy can be obtained.

&Quot; Vibrational urethane resin composition &

The damping urethane resin composition of the present invention (hereinafter also referred to as " the composition of the present invention ") contains a castor oil polyol (A), an isocyanate (B) and an inorganic particle (C) (D), the flame retardant (E) and the additive (F) within the range not to impair the effect of the present invention.

[Castor oil-based polyol (A)]

Castor oil is a pale yellow viscous oil derived from the seeds of a plant of the genus Chrysanthemum. In castor oil, about 90% of the fatty acids are ricinoleic acid, and they have hydroxyl groups, double bonds and ester bonds in one molecule. Examples of its properties include excellent stability, flexibility, electrical insulation, water resistance, and impact resistance. The composition of the present invention contains a castor oil-based polyol using castor oil having such characteristics as a starting material, so that a molded article having excellent heat resistance, hydrolysis resistance and acid resistance can be formed in addition to resistance to mechanical stress such as friction or impact .

Further, by using the castor oil-based polyol (A), a molded article hardly causing thermal deformation or hardening shrinkage can be formed.

In the case of a conventional vibration damping material, a polyether polyol or a polyester polyol is sometimes used. However, the inventors of the present invention have conducted intensive investigations. As a result, they have found that when a polyether polyol is used, the resulting molded article is too soft and the intended creep resistance tends not to be exhibited. Further, in the case of using a polyester polyol, The vibration damping property tends not to be manifested.

On the other hand, in the present invention, a molded article exhibiting the above effect can be obtained by using the castor oil-based polyol (A).

Examples of the castor oil-based polyol (A) include, but are not limited to, ester-exchanged products of one or more alkylene oxide adducts of castor oil and castor oil with at least one of alcohols, polyester polyols and polyether polyols; A fatty acid (a fatty acid obtained from a castor oil, which is usually a mixture of ricinoleic acid and oleic acid and the like) and at least one ester compound selected from the group consisting of alcohols, polyester polyols and polyether polyols; diol type partial dehydrated or partially acylated products of castor oil; A hydrogenated product of the ester compound, the ester compound, the ester compound, the ester compound and the compound of the partial dehydrate or the partial acyl compound, the polymerized castor oil is obtained by polymerizing the castor oil, the compound obtained by reacting the obtained transesterified oil of the castor oil with caprolactone .

As the castor oil-based polyol (A), a product synthesized according to a conventionally known method may be used, or a commercially available product may be used.

URIC H-102, URIC H-92, URIC H-81, URIC H-73X, URIC H-62, URIC H-420, URIC H-854, URIC H- 006, URIC Y-406, URIC HF-2009 (manufactured by Ito Corporation), HS CM-075P, HS PPE-12H, HS 3P-255, HS 3G-500B, HS 2B- 120, TLM, HS CM (manufactured by Hokoku K.K.), and the like.

The castor oil-based polyol (A) is not particularly limited, and examples thereof include polyols having a hydroxyl value of 30 to 400 mgKOH / g and a functional group number of 1 to 6. The above-mentioned castor oil-based polyol (A) is preferably a polyol having a hydroxyl value of 300 mgKOH / g or more and a functional group number of 3 or more, more preferably a hydroxyl value of 340 mgKOH / g or more and a functional group number of 3 or more . The upper limit of the hydroxyl value may be 400 mgKOH / g, and the upper limit of the number of functional groups may be 6. [

By using the castor oil-based polyol (A) having a hydroxyl value and a number of functional groups within the above range, a molded article excellent in vibration damping property and creep resistance can be obtained, a molded article having a high crosslinked density and high strength, . Also, by using the castor oil-based polyol (A) having a hydroxyl value and a functional group number within the above range, a molded article having a high loss coefficient even at a high temperature can be obtained.

The number of the functional groups represents the number of hydroxyl groups in one molecule of the castor oil polyol (A).

Specific examples of the castor oil-based polyol (A) having a hydroxyl value of 300 mgKOH / g or more and a functional group number of 3 or more include URIC H-102, URIC H-92 and URIC H-81 have.

The viscosity of the castor oil-based polyol (A) is preferably 8,000 mPa · s or less, more preferably 6,000 mPa · s or less, more preferably 3,000 mPa · s or less as measured at 25 ° C. by using a Ube load viscometer according to JIS Z8803 Or less. The lower limit of the viscosity of the castor oil-based polyol (A) is preferably 30 mPa · s, and more preferably 300 mPa · s.

The number average molecular weight (Mn) of the castor oil-based polyol (A) is preferably 4,000 or less, more preferably 2,500 or less, and particularly preferably 2,000 or less. The lower limit of the Mn of the castor oil-based polyol (A) is preferably 200, more preferably 300.

The above-mentioned Mn can be obtained by calculating based on the hydroxyl value of the castor oil-based polyol (A).

In general, the viscosity of the castor oil-based polyol (A) tends to increase as the Mn is larger.

By using the castor oil-based polyol (A) having a Mn or a viscosity in the above-mentioned range, a vibration-proof urethane resin composition exhibiting high fluidity even in a solventless form can be obtained and a molded article can be formed by pouring or the like.

The content of the castor oil-based polyol (A) is preferably 25 to 80 mass%, more preferably 30 to 70 mass%, and particularly preferably 35 to 60 mass% with respect to the total amount of the composition of the present invention. When the content of the castor oil-based polyol (A) is in the above range, a molded article excellent in creep resistance and vibration damping effect can be obtained.

The castor oil-based polyol (A) may be used alone or in combination of two or more.

[Isocyanate (B)]

The isocyanate (B) may be any compound that can be cured by reacting with the castor oil polyol (A). Examples of such isocyanates (B) include diphenylmethane diisocyanate (hereinafter, abbreviated as "MDI") such as 2,2'-MDI, 2,4'-MDI, 4,4'-MDI, (MDI)), tolylene diisocyanate (hereinafter abbreviated as "TDI" [eg 2,4-TDI, 2,6-TDI]) and naphthalene diisocyanate, hexamethylene diisocyanate, Aliphatic polyisocyanates such as isophorone diisocyanate and xylylene diisocyanate, carbodiimide-modified products of the polyisocyanate, and polyurethane-based prepolymers obtained by reacting an isocyanate compound with a low molecular polyol or the like.

Among them, it is preferable to use carbodiimide-modified isocyanate and / or TDI as isocyanate (B) because a molded product excellent in mechanical strength and creep resistance can be obtained. The carbodiimide-modified isocyanate is preferably a carbodiimide-modified MDI.

Since carbodiimide-modified MDI and TDI have a strong benzene ring as a structure and a flexible segment, by using these compounds, it is possible to obtain a molded article which is tough, has flexibility, and has excellent creep resistance and heat resistance.

As the isocyanate (B), a component containing the isocyanate may be used. The component may be synthesized by a conventionally known method, or a commercially available product may be used.

In addition, commercially available products may contain the above isocyanate as a main component, further include an isomer of the isocyanate or the like, or may contain a solvent. In the present invention, these commercially available products can be used without any particular limitation, but mechanical strength, creep resistance And is capable of forming a molded article which is less prone to thermal deformation and hardening shrinkage, and is preferably a solventless isocyanate.

Examples of commercially available products of carbodiimide-modified MDI include Millionate MTL (manufactured by Nippon Polyurethane Industry Co., Ltd.) and Loopranate MM-103 (manufactured by BASF INOAC Polyurethane Co., Ltd.) 80 (manufactured by Mitsui Chemicals, Inc.) or Loopranate T-80 (manufactured by BASF INOAC Polyurethane Co., Ltd.).

The isocyanate (B) in the composition of the present invention is preferably blended such that the equivalent ratio of the hydroxyl group of the castor oil polyol (A) to the isocyanate group of the isocyanate (B) is NCO / OH = 0.7 to 2, 1.5. When the equivalence ratio is within this range, it is preferable because it is hard to cause hardening defects or foaming, and it is also possible to obtain a molded article having high vibration damping effect, excellent resistance to compression load and impact resistance, and little plastic deformation due to heat.

The isocyanate (B) may be used alone or in combination of two or more.

[Inorganic Particles Containing Phase Change Substance (C)]

The inorganic particles (C) containing the phase-change material are not particularly limited as long as the particles contain a phase-change material in the interior of the inorganic particles. Specifically, the inorganic particles include microcapsules Or a particle in which a phase change material is filled in pores of a porous particle formed of an inorganic material. That is, the inorganic particles (C) may be in a state in which the phase-change material is completely covered with the outer periphery of the inorganic material, or in a state in which the phase-change material is captured in the pores of the porous material .

By using the inorganic particles (C), it is easy to be deformed by a load, so that a molded article which can easily convert vibration energy into thermal energy can be obtained. Therefore, the formed article is excellent in vibration damping effect, creep resistance and heat resistance.

In the case of a conventional vibration damping material, microcapsules having an outer periphery made of an organic resin such as melamine resin, acrylic resin or urethane resin are sometimes used. However, the inventors of the present invention have conducted intensive investigations, and as a result, they have found that such a microcapsule is difficult to be deformed because of its very strong outer shell structure. Therefore, when the microcapsule is used, it is difficult to convert vibration energy into heat energy, I did.

On the contrary, in the present invention, a molded body exhibiting the above effect can be obtained by using the inorganic particles (C).

Further, the composition of the present invention is different from a composition obtained by adding inorganic particles having pores and a phase-change material, respectively. In the case where the phase-change material is not contained in the inorganic particles as described above, it is difficult to uniformly disperse the phase-change material in the urethane resin composition, and the phase-change material is bleed-out from the obtained molded article to exhibit the desired damping property Tend not to.

On the other hand, in the case of the composition of the present invention, the particles (phase-change material) can be uniformly dispersed in the urethane resin composition by using the inorganic particles (C).

The porous particles formed of the inorganic particles or inorganic materials forming the shell are preferably those having a heat resistance temperature sufficiently higher than the melting point of the phase change material and having a strength in accordance with the use of the composition of the present invention, And inorganic particles having pores such as silica, calcium carbonate and talc.

The porous particles may be particles made of an inorganic material having pores penetrating from the surface to the inside thereof. The porous particles may be hollow particles having cavities in them, or particles having no cavities.

The phase change material preferably has a melting point between -30 and 200 ° C, preferably between 0 and 40 ° C. Examples of the phase change material include paraffins such as paraffinic hydrocarbons, waxes such as natural wax and petroleum wax, fatty acids such as capric acid and lauric acid, polyalkylene glycols such as polyethylene glycol and barium hydroxide octahydrate, strontium octahydrate , Sodium acetate trihydrate, magnesium acetate tetrahydrate, aluminum ammonium sulfate 12 hydrate, and the like. Of these, the phase-change material is preferably at least one selected from paraffin, wax, fatty acid and polyalkylene glycol. Particularly, it is preferable to use a material which causes a solid-liquid phase transition near the room temperature, that is, a paraffinic hydrocarbon having a melting point of 0 to 40 캜. Specific examples thereof include pentadecane, hexadecane, heptadecane, octadecane, And itaconic acid.

The phase-change material contained in the inorganic particles may be one type alone or two or more types.

The inorganic particles (C) may contain a substance other than the phase change material. Such materials include, for example, trapping materials that stably maintain the phase change material in the pores.

The average particle diameter of the inorganic particles (C) measured by a scanning electron microscope (SEM) is not particularly limited, but is preferably from 0.5 to 200 탆 from the viewpoint of excellent creep resistance and a molded article having a large loss coefficient. And more preferably from 1 to 150 mu m.

Commercially available inorganic particles (C) include Riken Resins LA-5-100, LA-15-100 and LA-25-100 (manufactured by MIKI RICHEN KOGYO CO., LTD.).

The content of the inorganic particles (C) is preferably in the range of 1 to 25 mass% with respect to the total amount of the composition of the present invention. When the inorganic particles (C) are used in such an amount, the creep resistance is excellent. Or more can be easily obtained. The content of the inorganic particles (C) is preferably from 6 to 25 mass%, and a molded article having an excellent creep resistance and a loss coefficient tan? Of 0.5 or more can be easily obtained by using the inorganic particles (C) in such amounts . If the content of the inorganic particles (C) is more than 25 mass%, the obtained molded article tends to be retreated, and if the content is less than 1 mass%, a molded article having excellent vibration damping property tends not to be obtained.

The inorganic particles (C) may be used alone or in combination of two or more.

[Inorganic pigment (D)]

The composition of the present invention may contain an inorganic pigment (D) in order to improve resistance to creep change. The inorganic pigment (D) is an inorganic material other than the inorganic particles (C). The inorganic pigment (D) may be used alone or in combination of two or more.

Examples of the inorganic pigment (D) include general extender pigments such as silica, talc, mica, potassium feldspar, wollastonite, kaolin, clay, bentonite, titanium oxide, zinc oxide, calcium carbonate, magnesium carbonate and barium sulfate .

Examples of commercially available inorganic pigments (D) include TK-1 (Silica, manufactured by Tonosun Mining Industry Cooperative Association), R-5N (titanium dioxide, manufactured by Sakai Chemical Industry Co., Ltd.), Super SS (calcium carbonate, NYCEOS 4W (wollastonite, manufactured by NYCO MINERALS, INC.), And the like, and the like can be given. have.

The particle diameter of the inorganic pigment (D) measured in accordance with JIS K 5101 Pigment Test Method, Part 14 is not particularly limited, but is preferably 1,000 占 퐉 or less from the viewpoint of obtaining a molded article having excellent creep resistance , More preferably not more than 500 mu m.

The content of the inorganic pigment (D) is preferably 0 to 30 mass% with respect to the total amount of the composition of the present invention, and more preferably 5 to 25 mass% from the viewpoint of improving the creep resistance of the resulting molded article. If it is contained in an amount exceeding 30% by mass, the vibration damping property of the obtained molded article tends to be lowered.

The content of the inorganic particles (C) and the inorganic pigment (D) is preferably within the above-mentioned ranges, but the total content of the inorganic particles (C) and the inorganic pigment (D) , It is preferably 1 to 55% by mass, more preferably 5 to 50% by mass with respect to the total amount of the composition of the present invention.

As the inorganic pigment (D), silica is particularly preferably used, and when blended in the range of 12 to 25 mass% with respect to the total amount of the composition of the present invention, the loss tangent 隆 of the damping urethane resin molded article is 0.6 or more So that the creep resistance can be improved without damaging the loss coefficient.

[Flame retardant (E)]

The composition of the present invention may contain a flame retardant (E) to improve the flame retardancy. The flame retardant (E) may be used alone or two or more thereof may be used.

Examples of the flame retardant (E) include an inorganic type, a halogen type, a phosphorus type, a melamine type, and a silicon type flame retardant. Among them, the halogen-based flame retardant containing at least one element selected from a bromine element and a chlorine element exhibits an excellent flame retarding effect. However, when a halogen-based flame retardant is used, when the molded article obtained from the composition of the present invention is burned, toxic gas may be generated at the time of burning. For this reason, it is preferable to use a non-halogen flame retardant as the flame retardant (E).

Further, the flame retardant may be in different states such as powder phase and liquid phase. When the liquid flame retardant is added to the composition, the mechanical strength of the molded body obtained from the composition may decrease or bleed out (bleed out) may occur. If a powdery flame retardant is added to a composition in a large amount, the physical properties inherent to the molded article may be impaired. Therefore, it is preferable to use a powdery flame retardant which exhibits a flame retarding effect in a small amount as the flame retardant (E).

As the flame retardant (E), phosphorus flame retardants and melamine flame retardants, which are non-halogen flame retardants in particular, are preferably used.

Examples of the phosphorus flame retardant include ammonium polyphosphate, phosphoric acid ester, phosphazene, red phosphorus, triphenyl phosphate (TPP), triallyl phosphate, triethyl phosphate, tricresyl phosphate (TCP), cresylphenyl phosphate, intumescent flame retardant And the like.

Examples of the melamine-based flame retardant include melamine, melamine cyanurate, and melamine phosphate.

When the molded article obtained from the composition containing the flame retardant (E) is burned, the flame retardant (E) in the molded article is foamed and the adiabatic expansion layer on the foam is formed on the surface of the molded article. As a result, the heat of the surface of the molded body is prevented from being transferred to the inside, while the supply of oxygen is blocked, so that the burning of the flame can be suppressed. For this reason, it is particularly preferable to use an expandable flame retardant as the combustion agent (E).

Examples of commercially available flame retardant (E) include Exolit AP422, Exolit AP423, Exolit AP462, Exolit AP750, Exolit AP760 (manufactured by CLARIANT), PHOSMEL200 (manufactured by Nissan Chemical Industries, Ltd.) 2100JC, ADEKA STAB 2200S (manufactured by ADEKA), and MC-4000 (manufactured by Nissan Chemical Industries, Ltd.) as a melamine-based flame retardant.

The content of the flame retardant (E) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and particularly preferably 5 to 15% by mass with respect to the total amount of the composition of the present invention. When the content of the flame retardant (E) is within the above range, a molded article excellent in creep resistance and excellent in flame retardancy with a large loss factor can be obtained.

[Additive (F)]

The composition of the present invention may further contain additives (F) other than the above (A) to (E). Examples of the additive (F) include a defoaming agent, a moisture adsorbent, a catalyst and other materials.

The additive (F) may be used alone or in combination of two or more.

<Defoamer>

It is preferable that no bubbles are present in the molded article in order to obtain a molded article having excellent creep resistance. For this reason, it is preferable to add a defoaming agent to the composition of the present invention.

Examples of the antifoaming agent include a silicone antifoaming agent and a mineral oil antifoaming agent, and there are an aqueous system, a solvent system and a solvent system. In the present invention, a silicone-based antifoaming agent is preferably used as the solvent-free antifoaming agent in order to suppress the shrinkage of the molded article. The antifoaming agent is preferably contained in an amount of 0 to 3 mass% with respect to the total amount of the composition of the present invention. A commercially available silicone-based antifoaming agent of the solvent-free type includes, for example, Dow Corning Toray SAG-47 (manufactured by Toray Dow Corning Co., Ltd.).

The antifoaming agents may be used alone or in combination of two or more.

<Moisture Absorbent>

In the case of forming a molded article from a composition containing moisture in the atmosphere or in the system that can be contained in the inorganic particles (C) or the inorganic pigment (D), there is a possibility that water reacts with isocyanate as a curing agent to foam. In order to suppress this foaming, it is preferable to remove moisture in the system, and therefore, it is preferable to incorporate a moisture adsorbent into the composition of the present invention.

The moisture adsorbent is preferably blended in the range of 0 to 10 mass% with respect to the total amount of the composition of the present invention.

The moisture adsorbent may be used alone or in combination of two or more.

The moisture adsorbent is not particularly limited as long as it has a water adsorbing ability, and conventionally known substances can be used. As a commercially available product of the moisture adsorbent, for example, a molecular sieve 4A powder (manufactured by Union Showa Co., Ltd.) can be mentioned.

<Catalyst>

The composition of the present invention may contain a catalyst promoting the reaction of the castor free polyol (A) and the isocyanate (B). Examples of such catalysts include tin carboxylates, amine catalysts, metal carboxylates other than tin, and 1,8-diazabicyclo [5,4,0] undecene-7 (DBU) salts. Examples of the tin carboxylate include dibutyltin dilaurate, dibutyltin diacetate and tin octylate. Examples of the amine-based catalysts include triethylamine, triethylenediamine and tetramethylbutane diamine, and tin Examples of the other metal carboxylates include cobalt octylate, manganese octylate and zinc octylate, and DBU salts include DBU-stearate, DBU-oleate and DBU-formate.

Examples of commercially available products of these catalysts include Gleck TL (DIC), DABCO 33-LV (Air Products Japan), Neostan U-28 (Nitto Kasei), and triethylamine Die cell production).

The catalyst is preferably contained in the range of 0 to 3 mass% with respect to the total amount of the composition of the present invention.

The catalyst may be used alone or in combination of two or more.

<Other materials>

The composition of the present invention may further contain, if necessary, a wetting agent, a surface conditioner, a rheology control agent, a leveling agent, a plasticizer, a solvent, etc. to the extent that the object of the present invention is not impaired.

These other materials may be used alone or in combination of two or more.

Further, according to the present invention, in the case of using the castor-free polyol (A) having a viscosity within the above range, a high-fluid composition can be obtained even in a non-solvent formulation, so that a molded article hardly causing thermal deformation or hardening shrinkage can be formed It is preferable that the composition of the present invention does not contain a solvent, but depending on the use, a solvent may be used for obtaining an additional high-fluidity composition.

The viscosity of the composition of the present invention measured at 23 ° C using a BM type viscometer is preferably 40,000 mPa · s or less, more preferably 30,000 mPa · s or less. A composition having such a viscosity is preferable because it is easy to form a molded article by pouring or the like by showing a high fluidity.

[Method for preparing damping urethane resin composition]

The composition of the present invention can be prepared by mixing the above components (A) to (C), and further optionally (D) to (F). The composition of the present invention is preferably of a two-part type comprising a subject containing the component (A) and a curing agent containing the component (B) in view of storage stability and the like. In this case, the inorganic particles (C) may be added to either the top or the curing agent, but it is preferable to blend them. The inorganic pigment (D), the flame retardant (E) and the additive (F) may be incorporated in either the subject or the curing agent, but the inorganic pigment (D) and the flame retardant (E) are preferably incorporated in the subject. The catalyst in the additive (F) is preferably blended in the subject.

The composition of the present invention can be prepared by mixing the above-mentioned subject and the above-mentioned curing agent.

When air is mixed at the time of preparing the above-mentioned subject or mixing of the subject and the curing agent, bubbles remain in the resulting molded article, which causes cracks or collapse. For this reason, it is preferable to reduce the mixing amount of air into the composition by performing the defoaming process at the time of preparation of the subject or stirring the mixture at a low rotation when mixing the subject and the curing agent.

&Quot; Vibrational urethane resin molded article &quot;

The vibration damping urethane resin molded article of the present invention (hereinafter also referred to as &quot; molded article of the present invention &quot;) is formed from the composition of the present invention.

Therefore, the molded article of the present invention has high vibration damping effect, excellent resistance to compression load and impact resistance, and little plastic deformation due to heat.

The molded article of the present invention preferably satisfies the following requirements (1) and (2).

(1) The loss factor (tan?) At 80 DEG C and 1 Hz is 0.4 or more

(2) a creep change rate of 25% or less when a load of 4.5 MPa is applied at 70 DEG C for one week

Further, it is more preferable that the molded article of the present invention satisfies the following requirement (3).

(3) The flammability meets the HB standard of UL94 standard.

[Loss Factor]

The loss factor is the ratio of the storage shear modulus (G ') to the loss shear modulus (G "), G" / G', denoted by tan δ and indicates how much the vibration energy is converted to thermal energy . The larger the value of tan?, the more the vibration energy is converted into the thermal energy, that is, the vibration damping effect. Tan delta at 80 DEG C and 1 Hz is preferably 0.4 or more, more preferably 0.5 or more, and particularly preferably 0.6 or more in view of obtaining a molded article having excellent vibration damping properties.

The loss factor can be measured specifically by the method described in the following examples.

[Creep change rate]

The resin-based material sometimes undergoes plastic deformation when it is continuously subjected to a large load for a long time under a high-temperature atmosphere, and this is called a creep change. When the load of 4.5 MPa is applied under an atmosphere of 70 캜 for one week, the smaller the creep change rate is, the better the better. The creep change rate is preferably 25% or less, more preferably 20% or less. If the creep change rate exceeds 25%, the molded body may be broken or cracked due to deformation.

The creep change rate can be specifically measured by the method described in the following examples.

The molded article having the loss factor and the creep change ratio can be easily formed by using the composition of the present invention.

[combustibility]

Urethane resins are generally classified as combustible resins because they are easily burned. In addition, the materials used for the ship are required to have flame retardancy in order to prevent the expansion of the flame by SOLAS (International Convention for the Safety of Life at Sea) treaty.

The UL94 standard (the specification of the American Combustion Test established by Underwriters Laboratories Inc.) is the most common certification criteria for combustibility for plastic materials. The combustibility of the molded article of the present invention can be evaluated using a HB (horizontal combustion) test, which is a method of evaluating a solid plastic material, and the molded article preferably satisfies the HB standard. The combustibility can be measured specifically by the method described in the following examples.

The molded article having flame retardancy can be formed, for example, by using a composition containing a flame retardant (E).

Specifically, the molded article of the present invention can be formed by a pouring method, an extrusion molding method, an injection molding method, or an RIM molding method using the composition of the present invention, and the composition of the present invention is applied onto a substrate by spray, roller, And then curing it.

Examples of the substrate include concrete, mortar, slate plate, plywood, tile, metal, glass, film and fiber, and these substrates may be surface-treated.

In particular, when the composition of the present invention having high fluidity is used, it is preferable to form the molded article of the present invention by directly pouring the composition into a place (construction site) where the molded article of the present invention is to be formed and curing. According to this method, it is possible to sufficiently fill the narrow gap even when the molded body is filled.

The molded article of the present invention can be suitably used for generating vibration such as a ship, an automobile, a railway, an aircraft, a building, an industrial device, a household appliance, and a precision instrument. The molded article is particularly suitable for use under a high-

The molded article of the present invention is particularly suitable for use in the lower portion of a marine engine, and can be suitably used under a view engine in the case of a marine engine equipped with a cycle engine and a view engine. This is because the molded article of the present invention is excellent in vibration damping property, so that the view engine can be protected from the vibration caused by the periodic engine at the time of non-operation of the view engine.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless specifically stated in the description of the examples below, &quot; part &quot; indicates &quot; part by mass &quot;.

[Production of urethane resin composition and molded article]

[Example 1]

80.0 parts of a castor oil polyol URIC H-102 (manufactured by Ito Kasei K.K.) and 20.0 parts of Lycan Resin LA-15-100 (manufactured by Mikkiken Kogyo K.K.) were placed in a container, Dispersion was carried out for 10 minutes at 500 rpm or less using a disper. Thereafter, 0.2 part of Dow Corning Toray SAG-47 (Toray Dow Corning Co., Ltd.), 3.0 parts of Molecular Sieve 4A powder (manufactured by Union Showa Co., Ltd.), 10 parts of Gleeve TL (DIC) 0.1 part were sequentially added and stirred to prepare a subject. Thereafter, 70.1 parts of Millionate MTL (manufactured by Nippon Polyurethane Industry Co., Ltd.) was added as a curing agent so as to have an NCO / OH ratio of 1.06, followed by mixing and defoaming to prepare a urethane resin composition.

The urethane resin composition after defoaming was poured into a molding die of 100 x 100 x 25 mm and cured at 23 占 폚 for 16 hours to manufacture a urethane resin molded article.

[Examples 2 to 17, Comparative Examples 1 to 7]

A urethane resin composition was prepared in the same manner as in Example 1 except that kinds and amounts of raw materials were changed as shown in Table 2 or 4, and a urethane resin molded article was produced in the same manner as in Example 1 except for using the obtained composition Respectively. The details of each material in Table 2 or Table 4 are shown in Table 1.

[Example 18]

80.0 parts of a castor oil-based polyol URIC H-81 (manufactured by Ito Oil Co., Ltd.) and Exolit AP462 (manufactured by CLARIANT) were placed in a 15.0 parts container and dispersed at 1,000 rpm for 15 minutes using a high speed dispenser. Thereafter, 20.0 parts of Riken Resin LA-15-100 (manufactured by MIKI RICHEN KOGYO CO., LTD.) Was blended and dispersed at 500 rpm or less for 10 minutes using a high-speed dispenser so as not to destroy the outer surface of the microcapsules. After completion of the dispersion process, 0.3 part of Dow Corning Toray SAG-47 (manufactured by Toray Dow Corning Co., Ltd.), 3.0 parts of Molecular Sieve 4A powder (manufactured by Union Showa Co., Ltd.) )) Were sequentially added and stirred to prepare a subject. 74.5 parts of Millionate MTL (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a curing agent was added thereto so as to have an NCO / OH ratio of 1.06, followed by mixing and defoaming to prepare a urethane resin composition.

The urethane resin composition after defoaming was poured into a molding die of 100 x 100 x 25 mm and cured at 23 占 폚 for 16 hours to manufacture a urethane resin molded article.

[Examples 19 to 25]

A urethane resin composition was prepared in the same manner as in Example 18 except that kinds and amounts of raw materials were changed as shown in Table 3. A urethane resin molded article was prepared in the same manner as in Example 18 except that the obtained composition was used. The details of each material in Table 3 are shown in Table 1.

[Measurement of loss coefficient]

The loss factor tan? Was measured using the urethane resin molded articles produced in Examples 1 to 25 and Comparative Examples 1 to 7. The loss factor was measured using a fatigue and durability test mode of "Shimazu servo pulser EHF-EG10-20L type" manufactured by Shimadzu Corporation, Shimadzu Corporation, and "Shimazu servo pulser 4830 type control device" as software. The test was carried out at a temperature of 80 占 폚, applying a load of 5 kN in the compression direction while applying a vibration of 1 Hz frequency to the urethane resin molded body, and repeating this cycle for 1,000 cycles. The coefficients were measured. The results of the loss factor were evaluated in the following four stages. The results are shown in Tables 2 to 4.

   4: 0.6? Tan?

   3: 0.5? Tan? &Lt; 0.6

   2: 0.4? Tan? &Lt; 0.5

   1: tan? &Lt; 0.4

Evaluations 2 to 4 were evaluated as acceptable ◯, and evaluation 1 was evaluated as unsatisfactory ×.

[Measurement of creep change rate]

Using the urethane resin compositions obtained in Examples 1 to 25 and Comparative Examples 1 to 7 in the same manner as in Example 1 or Example 18 except that a molding die of 100 × 100 × 5 mm was used as the molding die, Respectively. The formed urethane resin molding was cured by the method according to ASTM D621. After curing, four specimens of 5 x 5 x 5 mm in size were cut out from the compact, and a load of 4.5 MPa was applied to the specimen in the thickness direction of the specimen in an atmosphere of 70 DEG C for one week. The thickness of the test piece was measured before application of the load and after one week from the application of the load, and the rate of change of the test piece in the thickness direction before and after the application of the load was calculated. The rate of change was similarly measured for each of the four test specimens, and the average value was defined as the creep change rate. The creep change rate was evaluated in the following three stages. The results are shown in Tables 2 to 4.

   3: creep change rate &lt; 20%

   2: 20? Creep change rate? 25%

   1: Deformation immediately after the specimen undergoes fracture or load

Evaluations 2 and 3 were evaluated as acceptable ◯, and evaluation 1 was evaluated as unacceptable.

[Evaluation of flammability]

The urethane resin compositions obtained in Examples 3 and 18 to 25 were used in the same manner as in Example 1 or Example 18 except that a molding die of 150 × 125 × 1 mm was used as the molding die. Thereafter, the molded body was processed into dimensions of 127 mm in length and 12.7 mm in width to obtain a test sample. The test specimens were drawn at 25 mm and 100 mm in length from one end to the other. Five specimens were produced. The test specimens were held at 23 ° C and 50% relative humidity for 48 hours and then tested.

Based on the HB (horizontal combustion) test procedure of the UL94 standard, the test was carried out five times in the following manner to evaluate the flammability.

Test specimens meeting the HB criteria,

1. When the thickness of the specimen is from 3.0 mm to 13 mm, the burning speed between 75 mm spans should not exceed 40 mm / min,

2. If the thickness of the specimen is less than 3.0 mm, the burning speed between 75 mm spans shall not exceed 75 mm / min, or

3. Regardless of the thickness of the specimen, combustion should stop before reaching the 100 mm mark

This is the condition.

In the case of this test, since the thickness of the specimen produced is 1 mm, the burning speed between 75 mm spans should not exceed 75 mm / min, or burning should stop before the 100 mm mark is reached. .

In the test method, the test specimen was fixed at the farthest end from the 25 ㎜ mark of the test specimen, and the longitudinal direction of the specimen was horizontal and the width direction was inclined at 45 degrees. Then, the flame of the burner was brought into contact with the end of the test object where the test object was not fixed for 30 seconds, and then the burner was removed. In addition, when the tip of the burned burner reached the mark of 25 mm within 30 seconds from the contact of the flame of the burner, the burner was immediately separated from the specimen. The burning rate was determined by measuring the time in seconds when the burning tip reached the 25 mm mark and the burning time was 0 seconds after the flame was removed. If the burning stops after the flame is removed, measure the point where the combustion stops. The results of the combustibility test were evaluated in the following three stages. The results are shown in Tables 2 to 4. In addition, the results shown in Tables 2 to 4 are evaluated as "3" in the case of satisfying "3" in all of the five tests, and "3" in the case of evaluating "2" &Quot; That is, the results shown in Tables 2 to 4 indicate the lowest evaluation results among the five tests.

3: Burning rate ≤75 mm / min, and burning stopped before reaching 100 mm mark

2: Burning stops before reaching the burning rate ≤ 75 mm / min, or 100 mm

1: Combustion rate> 75 mm / min, also burned to 100 mm mark

Evaluations 2 and 3 were evaluated as acceptable ◯, and evaluation 1 was evaluated as unacceptable.

Claims (16)

A damping urethane resin composition comprising a castor oil-based polyol (A), an isocyanate (B) and an inorganic particle (C) containing a phase-change material. The method according to claim 1,
Wherein the hydroxyl value of the castor oil-based polyol (A) is 300 mgKOH / g or more and the number of functional groups is 3 or more. The method according to claim 1,
Wherein the viscosity of the castor oil-based polyol (A) at 25 占 폚 is 8,000 mPa 占 퐏 or less. The method according to claim 1,
Wherein the inorganic particles (C) are contained in an amount of 1 to 25 mass%. The method according to claim 1,
Wherein the phase change material is at least one selected from paraffin, wax, fatty acid and polyalkylene glycol. The method according to claim 1,
Wherein the phase-change material has a melting point of -30 to 200 ° C. The method according to claim 1,
Wherein the isocyanate (B) is at least one selected from carbodiimide-modified diphenylmethane diisocyanate and tolylene diisocyanate. The method according to claim 1,
Further comprising an inorganic pigment (D). The method according to claim 1,
Further comprising a flame retardant (E). The method according to claim 1,
Further comprising an additive (F). The method according to claim 1,
2-part type vibration damping urethane resin composition. A damping urethane resin molded article formed from the vibration damping urethane resin composition according to any one of claims 1 to 11. 13. The method of claim 12,
A vibration damping urethane resin molded article satisfying the following requirements (1) and (2).
(1) The loss factor (tan?) At 80 DEG C and 1 Hz is 0.4 or more
(2) a creep change rate of 25% or less when a load of 4.5 MPa is applied at 70 DEG C for one week 14. The method of claim 13,
And satisfies the following requirement (3).
(3) The flammability meets the HB standard of UL94 standard. 13. The method of claim 12,
A vibration damping urethane resin molded article used under the engine of a ship. A method for forming a vibration damping urethane resin molded article, comprising the step of pouring the vibration damping urethane resin composition according to any one of claims 1 to 11 into a construction site to form a molded article.